JPH0468006A - New copolymer and stainproofing agent - Google Patents

Abstract

PURPOSE:To obtain a copolymer which can give a stainproofing agent excellent in initial water repellency and stain release and improved in durability and comprises structural units derived from three specified compounds containing specified fluorine compound. CONSTITUTION:A copolymer is obtained by using structural units derived from a fluoroalkyl (meth)acrylate (e.g. a compound of formula I), structural units derived from a polyalkylene glycol (meth)acrylate [e.g. a compound of formula II (wherein (p) is 3-9) and structural units derived from an epoxy (meth)acrylic ester (e.g. a compound of formula III). This copolymer can give a stainproofing agent excellent in initial water repellency and stain release and improved in durability.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel copolymer useful as an antifouling agent.
-Ro.

1. Prior art 2. Acrylic acid ester or methacrylate containing fluoroargyl ester is used as an anti-staining agent to impart water and oil repellency to textile fabrics and to make it easier to remove stains adhering to the fibers by washing. Copolymers of acid esters (hereinafter also referred to as fluorine-containing compounds) and hydrophilic group-containing compounds are known.

In order to improve various properties such as durability, flexibility, and texture, it is known to appropriately select polymerizable compounds and copolymerize them (Japanese Unexamined Patent Publications No. 53134786, No. 59). -204980).

[Problems to be Solved by the Invention] However, the conventional antifouling agents as described above have insufficient water repellency and durability against washing, and have not yet achieved satisfactory performance. In addition, various polymerizable compounds have been studied to improve durability, but no antifouling agent with improved durability has yet been developed.

The object of the present invention is to improve the above-mentioned drawbacks and to provide an antifouling agent that has excellent initial water repellency and dirt releasability, and has improved durability.

[Elaborate Means for Solving the Problems J] The present invention provides a structural unit derived from (a) an acrylic ester or a methacrylic ester containing a fluoroalkyl group, (b) a polyalkylene glycol acrylate or a polyalkylene glycol methacrylate. and (c) a structural unit derived from an acrylic ester or a methacrylic ester containing an epoxy group, the amount of the structural unit (a) relative to the copolymer. is 30 to 82% by weight, the amount of the structural unit (b) is 15 to 67% by weight, and the amount of the structural unit (C) is 3 to 55% by weight. The present invention also provides an antifouling agent containing the copolymer as an active ingredient.

Preferably) monomers forming the structural unit (a) have the general formula %) where Rf is a linear or branched perfluoroalkyl group having 3 to 20 carbon atoms; R1 is a linear or branched alkylene group having 1 to 10 carbon atoms, -5OPN(R3)R'- group or -CH2CH(O
R5) CH2- group (wherein R3 is an alkyl group having 1 to 10 carbon atoms, R' is a linear or branched alkylene group having 1 to 10 carbon atoms, R5 is a hydrogen atom or 1 Anru group with ~10 carbon atoms),
R2 represents a hydrogen atom or a methyl group. ] It is a compound represented by Examples of such monomers include the following.

CF3(CF2)7(CH2)loOCOCH=CH2
CF3 (CF2), (CH2),. 0COC(CH3)
・CH2CF3(CF2)8CH20COCH=CH2
CF3 (CF2). C1120COC(CHt3)・C
H7(CF3), cF(CF2)e(CH2), 0cO
cH-CF2(CF3)2CF(CF,)8(C112
), 0COCII・C) [2(CF3)=CF(CF2
)1o(Ct(2)20cOcH・CF7(CF3)2
CF(CF2)6(CH2)20COC(CH3)・C
H7(CF3)2cF(CF2)e(CHt)20cO
c(CH3)・CH.

(CF+)2CF(CF,)1o(CH2)tOCOC
(CH3)CH2CF3CF2(CF2)s(CH2)
,0COCR=CHtCF3CF2 (CF2)
8(CH2) 20COCR-CH2CF3CF2(C
F2), 0(CH2)20COCH=CH2CF3CF
2 (CF,)6(CH2) 20COC(CH3)・
CH.

CF, CF t (CF 2) B (CI-) 20c
Oc(CH3)=CH2CF3CF2 (CF2),
o(cHt) 20COC(CH3)=CH2CF3
(CF2)7S021T(CH3)(CH2), 0CO
CH-CH2CF3(CF2)7SO7N(C7H5)
(CH2)zOcOc(CHt)”CH2(CF3)2
CF(CF2)8CH,CI((OCOCH3)C)1
．． 0cOc(CH3)・CH3(CF3)2CP(CF
2), CH2C1((OH)CH3OCOCH=CH2
Preferred monomers forming the structural unit (b) have the general formula %)87, where R6 is a hydrogen atom or a methyl group, R7 is an alkylene group having 2 to 6 g of carbon atoms, and R8 is a hydrogen atom or a carbon Number 1
~20 alkyl groups, n represents an integer of 3 to 50. It is a chemical compound that can be expressed as a chemical compound. R7 is usually CH2C
Particularly good results are obtained when H2- or CH3C2Hs CHCI (2CHCH2- may also be used. Of course, a mixture of two or more different types of R7 and n may be employed. Examples of monomers forming the structural unit (b) include the following.

CH2=CHC00(CH2CH20)l)H(p-3
~9) CH, ・C(CH3)Coo(CH7CH20)
pH (p=3-9) CH2・CHCOO(CH2CF3
O) pci+3 (p=3~9)CH3=C(C
H3) Coo(CH,CH20)pCH3(p=3~
9) CH2・C(C)13)C00(C11,C)12
0)2. CH3CH2・C(CH3)C00(CH2C
H2)8HCH3 CH, ・C(CH3)Coo(CH2CHO) 12H
H3 CH2=CHCOO(CH2CHO) , , CH3
CH3 CH7・C(CH3)C00(CH2CH20)5(C
H2CHO)3HH3 A preferred monomer forming the structural unit (c) has the general formula [wherein R8 is a hydrogen atom or a methyl group, and R'' is a direct bond or a straight line having 1 to IO carbon atoms. Chain or branched alkylene group, R'' is a hydrogen atom or 1 to 10
A straight chain chain having 1 carbon atoms indicates a branched alkyl group. ] It is a compound represented by. Examples of such monomers include the following.

CI-(2=CHCOOCH-CH2X1Cl-1,=C(CH3)C00Cf-1-CH2X
1 Cf-12= CHCOOCH2CH-CH2N 1 CI-(2=C(CH3)CH2CH2CH-CH2X
1 CH2=CHCOOCH2CH, CH-CFIC, H,
,\ / ○ CH2=C(CH3)C00CH,CI(2CH-CH
2X 1 CH3-CHCoo(CH2), CH-CI(CH2X
1 Each of the structural units (a), (b) and (c) is 2
It may also be formed from a mixture of more than one type of monomer.

The amount of structural unit (a) is from 30 to 82% by weight, preferably from 40 to 70% by weight, based on the copolymer.

If it is less than 30% by weight, water and oil repellency is not sufficient. The amount of structural unit (b) is 15 to 67% by weight, preferably 25 to 50% by weight, based on the copolymer. If it is less than 15% by weight, the stain releasability will not be sufficient. The amount of structural unit (c) is 3 to 55% by weight, preferably 5 to 20% by weight, based on the copolymer. If it is less than 3% by weight, the stain releasability and durability will not be sufficient.

The copolymer in the present invention has the above-mentioned structural units (a) and (b).
) and (C), further ethylene, vinyl chloride,
Contains no fluoroalkyl groups such as vinylidene halides, styrene, acrylic acid and its alkyl esters, methacrylic acid and its alkyl esters, hensyl methacrylate, vinyl alkyl ketones, vinyl alkyl ethers, butadiene, isoprene, chloroprene, maleic anhydride It may also contain other structural units derived from polymerizable compounds. As a result, in addition to water and oil repellency, durability, and flexibility, a cost-effective copolymer can be obtained, or solubility, water pressure resistance, and various other properties can be appropriately improved. However, the amount of such other structural units is preferably 5% by weight or less based on the copolymer.

In order to obtain the copolymer of the present invention, various polymerization reaction methods and conditions can be arbitrarily selected, and various polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, and radiation polymerization can be used. Either of them can be adopted. For example, a method may be employed in which a mixture of compounds to be copolymerized is emulsified in water in the presence of a surfactant and copolymerized while stirring. Various types of peroxide, azo, and persulfate initiators can be used as the polymerization initiator in the reaction system. Polyalkylene glycol acrylate or methacrylate acts as a surfactant, so there is no need to use a surfactant.
Various anionic, cationic or nonionic emulsifiers may be added to the color combination.

Dissolve the raw material monomer in a suitable organic solvent and add a polymerization initiation source (
Solution polymerization can also be carried out by the action of peroxides, azo compounds, or ionizing radiation, which are soluble in the organic solvent used. Suitable solvents for solution polymerization include isopropanol, edil cellosolve, trichlorotrifluoroethane,
These include tetrafluorofluoroethane and methylchloroform.

The copolymer thus obtained is processed into an emulsion,
The antifouling agent can be prepared in any form such as a solvent solution or an aerosol.

The method of applying the antifouling agent containing the copolymer of the present invention as an active ingredient should be selected depending on the type of material to be treated, the purpose of use, the preparation form of the antifouling agent, etc. good. In the case of an aqueous emulsion or a solvent solution type, it may be applied to the surface of the object to be treated by a known method such as spraying, dipping, or coating, followed by drying, and curing may be performed if necessary. In addition, in the case of an aerosol type, it may be sprayed onto the object to be treated and allowed to dry. Furthermore, an antistatic agent, a flame retardant, an anti-wrinkle agent, and other polymers may be added to the copolymer of the present invention, if necessary.

The objects to be treated with the copolymer of the present invention include cotton, linen,
Manufactured by using various fibers such as animal and vegetable natural fibers such as silk and wool, synthetic fibers such as polyamide, polyester, polyacrylonitrile, and polyhinyl alcohol, and semi-synthetic fibers such as cellulose acetate and acetate, either alone or by blending these fibers. Examples include yarn, woven fabric, knitted fabric, felt, nonwoven fabric, paper, wood, leather, and the like. When the object to be treated is yarn or cloth, the amount of copolymer applied is usually 100% of the object to be treated.
It is 1 to 10 parts by weight of O.

Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples, but it goes without saying that this explanation does not limit the present invention. % means weight % unless otherwise specified.

The water repellency and oil repellency shown in the following Examples and Comparative Examples were tested using the following test method. Water repellency was determined by the JISL-1092 spray method (see Table 1 below), and oil repellency was determined by placing the test solution shown in Table 2 below on the test cloth at 0.05zQ, and determining the state of penetration after 30 seconds. Judgment (A A TCCTMI 18-1983).

As shown in Table 1, the soil removability (SR property) test is conducted as follows. Spread the test cloth on a filter paper laid horizontally, add 1 drop of waste motor oil, put a polyethylene notebook on top of it, put a weight on 2 and 9, and after 60 seconds, remove the weight and polyethylene. After removing the notebook and leaving it at room temperature for 1 hour, wash it with detergent (Super Zabu, brand name) 6 in an electric washing machine.
09, weight 35C, wash at 140℃ for 10 minutes, rinse,
Air dry. The dried test fabrics are designated by the appropriate grade (see Table 3).

Table 3 Judgment grade Judgment standard 1.01 Significant fleas remaining 2.01 Significant fleas remaining Example 1 CF 3CF 2 (CF 2 CF 2 ) n C
Compound 709 represented by H2CH20COCH=CH3 (mixture of compounds with n=3.4.5 in a weight ratio of 5:31)
, CH2=C(CH3)C00(CH2Cl,0)9C
H3259, CH2=C(CH3)C00CH-CH2
59, ＼ 1 Place 1 cup of isopropanol 4009 in a glass neck flask (inner volume LO) equipped with a mercury thermometer and a polytetrafluoroethylene crescent-shaped blade stirrer, and thoroughly disperse it by stirring under a nitrogen stream. After further cleaning by nitrogen blowing for about 1 hour, 1.09 g of azobisisobutyronitrile was added, and the mixture was further heated at 70° under nitrogen atmosphere A.
The copolymerization reaction was carried out by stirring for 10 hours at 40°C. Gas chromatography showed that the conversion rate of the copolymerization reaction was 99% or more. It was found that the ratio of each structural unit in the copolymer obtained from this conversion rate almost matched the ratio of the charged f-comonomer. The resulting dispersion contained 20% copolymer solids.

This copolymer dispersion was diluted with water to give a copolymer solid content of 0.5% by weight. Dip polyester cloth, 35% cotton, 65% polyester blend cloth, cotton cloth, and nylon cloth into this, squeeze it with a roll, and apply a wet pick amplifier for 70 minutes.
It was set to 0%. Next, dry with IoooC for 3 minutes, and then dry for 1
Heat treatment was performed at 60°C for 1 minute. The polyester fabric treated in this way has a water repellency of 90, an oil repellency of 8,
It showed stain releasability of 5. Durability was measured by repeating the same washing as in the stain removal performance test. After 5 washes, the water repellency was 70, the oil repellency was 6, and the stain removal was 4. The performance of other fabrics is described in Section 5.6 above.
It is shown in Table 7.

Examples 2 to 8 A dispersion of a copolymer having the composition shown in Table 4 below, prepared in the same manner as in Example 1, was diluted with water so that the copolymer solid content was 0.5% by weight. Using these diluted solutions, polyester cloth, a blended fabric of 35% cotton and 65% polyester, cotton cloth, and nylon cloth were treated in the same manner as in Example 1. The treated fabric had the performance shown in Table 56.7 above.

Comparative Examples 1 to 3 Copolymers having the compositions shown in Table 4 below, which were produced in the same manner as in Example 1, were evaluated in the same manner as in Example 1. The results are shown in Table 5.6.7 above.

1 Example 4 BrFA (40) G A (10) Table 4 40G (20) E Example 7 BrFA (60) 230G (20) P SPA is 1. CF3CP, (CP2CF2)nCH,C
H20COCH=CH2 (mixture of compounds with n=3.4.5 in a weight ratio of 5.3 I), SFMA is CF, CF2
(CF, CF2) ncH2cH20cOc(CH,)=
CH2 (mixture of n-3,4,5 compounds in weight ratio 5:3:l), BrFA, (CF3)2CF (CF
2CF 2)nCHtCH20COCH=CH2(n=
3.4.5 compounds in a weight ratio of 5:3:I), M
-90G is CH2C(CH3)C,0O(CH,CH
tO), CH,, PE350 is CH2-C(CH3)
Coo(CH2CH70) e H, M 40 G
IiCH2-〇 (CH3) COO(CH2CH20
), CH3, PE-200 is CH,=C(CH3)C
oo(CHzCHtO)sH,PP 800 is CH
2=C(CH3)C00(CH2CH2), 2H.

CH3 M-230G is CHt = C(CH3) COO(
CH2CH-0)23CH3, PP-500 is CH2
C(CH3) COO(CHt CHO) e HSG
M A is ＼ / Table 6 (Oil repellency test results) Table 5 (Water repellency test results) Table 7 (Stain removal test results)

Claims (1)

[Claims] 1. (a) a structural unit derived from an acrylic ester or a methacrylic ester containing a fluoroalkyl group; (b) a structural unit derived from a polyalkylene glycol acrylate or a polyalkylene glycol methacrylate; and (c) a copolymer consisting of a structural unit derived from an acrylic ester or a methacrylic ester containing an epoxy group, wherein the amount of the structural unit (a) is 30 to 82% by weight based on the copolymer. , a copolymer in which the amount of the structural unit (b) is 15 to 67% by weight, and the amount of the structural unit (c) is 3 to 55% by weight. 2. An antifouling agent containing the copolymer according to claim 1 as an active ingredient.